KR100457251B1 - microcapsule type insecticide and preparation process thereof - Google Patents
microcapsule type insecticide and preparation process thereof Download PDFInfo
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- KR100457251B1 KR100457251B1 KR10-2002-0016825A KR20020016825A KR100457251B1 KR 100457251 B1 KR100457251 B1 KR 100457251B1 KR 20020016825 A KR20020016825 A KR 20020016825A KR 100457251 B1 KR100457251 B1 KR 100457251B1
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- insecticide
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- oil
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- 239000002917 insecticide Substances 0.000 title claims abstract description 45
- 239000003094 microcapsule Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 6
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 20
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012047 saturated solution Substances 0.000 claims abstract description 3
- 238000009738 saturating Methods 0.000 claims abstract description 3
- 230000005611 electricity Effects 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000575 pesticide Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000005944 Chlorpyrifos Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920000954 Polyglycolide Polymers 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920001983 poloxamer Polymers 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- HTRXGEPDTFSKLI-UHFFFAOYSA-N butanoic acid;ethyl acetate Chemical compound CCCC(O)=O.CCOC(C)=O HTRXGEPDTFSKLI-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000002775 capsule Substances 0.000 abstract description 28
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 24
- 239000012071 phase Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002088 nanocapsule Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
본 발명은 마이크로캡슐 형태의 살충제 및 이의 제조방법에 관한 것으로서 보다 상세하게는 캡슐 내부의 활성물질로 살충제오일을 포함하며 살충제오일을 감싸는 캡슐의 외부 벽재는 생분해성 고분자로 구성되는 마이크로캡슐 형태의 살충제 및 이의 제조방법에 관한 것이다.The present invention relates to a microcapsule-type insecticide and a method for manufacturing the same, and more particularly, to an insecticide oil as an active substance inside the capsule, and the outer wall of the capsule surrounding the insecticide oil is a microcapsule-type insecticide composed of a biodegradable polymer. And it relates to a manufacturing method thereof.
마이크로캡슐 형태의 살충제 제조방법은 생분해성 고분자 0.1∼1.0 중량부를 용매 10∼20 중량부에 용해시킨 후 살충제오일 0.001∼0.01 중량부를 혼합하는 단계와,In the method of preparing a microcapsule insecticide, 0.1 to 1.0 parts by weight of a biodegradable polymer is dissolved in 10 to 20 parts by weight of a solvent, followed by mixing 0.001 to 0.01 parts by weight of an insecticide oil,
전기의 생분해성 고분자와 살충제오일이 혼합된 용액을 안정화제 0.5∼5 중량부가 용해되어 있는 수용액 20∼30 중량부에 포화시키는 단계와,Saturating the solution containing the biodegradable polymer and insecticide oil in an amount of 20 to 30 parts by weight in an aqueous solution in which 0.5 to 5 parts by weight of a stabilizer is dissolved;
전기의 포화된 용액을 유화시키는 단계와,Emulsifying the saturated solution of electricity,
전기의 유화된 용액에 물 40∼80 중량부를 첨가하여 용매를 수상으로 확산시키는 단계와,Adding 40 to 80 parts by weight of water to the former emulsified solution to diffuse the solvent into the aqueous phase,
공지의 방법을 이용하여 잔존하는 용매를 제거하는 단계를 포함하는 것을 특징으로 한다.It is characterized by including the step of removing the remaining solvent using a known method.
Description
본 발명은 마이크로캡슐 형태의 살충제 및 이의 제조방법에 관한 것으로서 보다 상세하게는 내부의 활성물질로 살충제오일을 포함하며 살충제오일을 감싸는 캡슐의 외부 벽재는 생분해성 고분자로 구성되는 마이크로캡슐 형태의 살충제 및 이의 제조방법에 관한 것이다.The present invention relates to a microcapsule-type insecticide and a method for preparing the same, and more particularly, to an insecticide oil as an active substance therein, and an outer wall of the capsule surrounding the insecticide oil includes a microcapsule-type insecticide composed of a biodegradable polymer and It relates to a manufacturing method thereof.
일반적으로 캡슐(capsule)이란 천연 또한 합성 고분자로 만들어진 미소한 용기를 의미하고 있는 말로서 보통 크기에 따라 나노캡슐, 마이크로캡슐, 알갱이(bead)로 나누어져 부르고 있으며 이러한 캡슐은 어떤 물질을 주위 환경으로부터 보호하고, 실제로 활용하고자 하는 조건에서 내부물질의 활성을 나타낼 수 있거나, 내용물의 성질을 변화시키는 기능도 가지고 있다. 또한 고농도, 고활성 물질에 대하여 농도 및 활성을 일정하게 하며 요구되는 조건에서 서서히 방출시킬 수도 있는 막 투과 제어기능을 할 수 있어서 이러한 기능을 이용하여 휘발성 물질의 장기보관 및 색소의 안정화를 위하여 사용할 수 있고 맛과 냄새의 마스킹(masking)도 시킬 수 있으며 내부 물질의 방출제어 기능이 있으므로 물질의 독성을 감소시킬 수도 있다.In general, a capsule is a micro container made of a natural or synthetic polymer, and is generally divided into nanocapsules, microcapsules, and beads according to their size, and these capsules protect a substance from the environment. In addition, it can show the activity of the internal material under the conditions to be actually used, or has the function of changing the properties of the contents. It can also be used for long-term storage of volatiles and stabilization of pigments by using a function to control membrane permeation that can be released slowly under required conditions. It can mask the taste and smell, and also control the release of internal substances, thus reducing the toxicity of the substances.
캡슐을 제조하는 방법에는 계면중합법, 인-시튜(In-Situ) 중합법, 분무캡슐중합법, 다중에멀전중합법, 유화-확산 중합법등이 있으나 본 발명에서는 캡슐제조시에 가장 유리한 섞이지 않는 두 상(O/W)을 강제 유화시킨 후 농도 차에 의해 활성물질과 함께 섞여 있던 액이 수상으로 분산 되어 고분자 캡슐이 형성되는 유화-확산 중합법을 이용하여 마이크로캡슐 형태의 살충제를 제조하였다. 또한, 가장 보편적으로 사용되고 있는 에어로졸 형태, 플라스틱 캡 안에 적당한 먹이나 살충제를 배합한 독먹이법 형태, 그리고 조그마한 캔에 살충제를 넣어 연막에 의해 살충시키는 훈연법 형태등이 있으나 이러한 살충제는 적용할 수 있는 범위가 한정 되고, 한 번 살포 후 약효의 지속성이 오래 가지 않고, 살포시 유해한 유기용매의 불쾌한 냄새로 인하여 불편한 점이 많았다. 이러한 단점을 보완하고자 본 발명을 통해 생분해성 고분자인 폴리카프로락톤을 사용하여 유화-확산공정을 통해 살충제오일을 함유하는 수분산 마이크로캡슐라텍스 형태의 살충제를 사용함으로써 한 번의 살포시 약효의 지속성이 우수하여 적은 양을 사용하게 되어 경제적이며 물을 매질로 하였으므로 유기 용매의 냄새에 대한 단점을 극복하였다.Methods for preparing capsules include interfacial polymerization, in-situ polymerization, spray capsule polymerization, multiemulsion polymerization, emulsion-diffusion polymerization, and the like. After the forced emulsification of the phase (O / W), a microcapsule-type insecticide was prepared by using an emulsion-diffusion polymerization method in which a liquid mixed with the active material was dispersed into an aqueous phase by a concentration difference to form a polymer capsule. In addition, there are aerosol forms that are most commonly used, poisonous forms containing proper food or pesticides in plastic caps, and smoked forms in which insecticides are put in small cans by smoke screens. It was limited, and the sustainability of the drug did not last long after spraying, and there were many inconveniences due to the unpleasant smell of harmful organic solvents during spraying. In order to compensate for these drawbacks, through the present invention, using a biodegradable polymer polycaprolactone through the emulsification-diffusion process using an insecticide in the form of a disperse oil microcapsuletex containing insecticide oils excellent sustainability of the drug in one spraying It is economical to use a small amount of water as a medium to overcome the disadvantages of the smell of the organic solvent.
캡슐에 의한 살충제 제조 공정에 관한 구체적인 예는 대한민국 공개특허특2000-0028283호와 특1999-0066935호가 있으나 제조물의 제조 공정 방식에 있어 대한민국공개특허 특2000-0028283는 단순 혼합 및 교반에 의한 방식이고, 대한민국공개특허 특1999-0066935는 계면중합에 의한 공정 방식이며, 사용된 캡슐의 벽재도 본 발명에 사용된 것과 다르므로 그 제조물과 제조공정에 있어 본 발명과는 다른 기술적 특성이 다르다.Specific examples of the pesticide manufacturing process using capsules include Korean Patent Publication Nos. 2000-0028283 and 1999-0066935, but Korean Patent Application Publication No. 2000-0028283 is a method of simple mixing and stirring. Korean Patent Laid-Open Publication No. 1999-0066935 is a process method by interfacial polymerization, and since the wall material of the capsule used is also different from that used in the present invention, its technical characteristics are different from those of the present invention in its preparation and manufacturing process.
본 발명은 상기한 종래 기술의 문제점을 해결하기 위해 제안된 것으로써, 본 발명은 생분해성 고분자를 사용하여 유화-확산공정을 통해 살충제오일을 함유하는 수분산 마이크로캡슐 형태의 살충제 및 이의 제조 공정의 제공을 목적으로 한다.The present invention has been proposed to solve the above problems of the prior art, the present invention is a pesticide in the form of water-dispersible microcapsules containing pesticide oil through an emulsification-diffusion process using a biodegradable polymer and a process for producing the same It is for the purpose of providing.
본 발명의 생분해성 고분자를 이용한 수분산 마이크로캡슐 형태의 살충제는 마이크로캡슐 공정을 통해 생분해성 고분자를 벽재로 사용하여 살충제오일의 유해하고 불쾌한 냄새를 마스킹하면서 약효의 효과가 오래 지속되도록 함과 동시에 물을 용매로 사용하기 때문에 환경오염 문제를 해결하는 환경 친화적인 살충제 캡슐로서 환경문제 해결과 더불어 일반적으로 사용의 폭이 한정 되었던 에어로졸 형태, 매트 형태, 독먹이법 형태 그리고 훈연법 형태의 단점을 보완하여 그 응용 범위를 확대 시킬 수 있다.Insecticide in the form of water-dispersed microcapsules using the biodegradable polymer of the present invention by using the biodegradable polymer as a wall through the microcapsule process while masking the harmful and unpleasant odor of the pesticide oil while maintaining the long-term effects of the drug and water It is an environmentally friendly insecticide capsule that solves environmental problems because it uses solvent as a solvent, and it solves environmental problems and supplements the disadvantages of aerosol form, mat form, poisoning form and smoking form, which have been limited in general. Its application scope can be expanded.
도 1은 본 발명의 마이크로캡슐 형태의 살충제 사진이다.1 is a photograph of a pesticide in the form of microcapsules of the present invention.
본 발명의 마이크로캡슐 형태의 살충제는 캡슐 내부의 활성물질로서 살충제오일을 포함하며 살충제오일을 감싸는 캡슐의 외부 벽재는 생분해성 고분자로 구성됨을 특징으로 한다.The insecticide in the form of microcapsules of the present invention includes an insecticide oil as an active substance inside the capsule, and an outer wall of the capsule surrounding the insecticide oil is characterized by being composed of a biodegradable polymer.
본 발명에서 살충제오일은 일반적으로 살충제의 원료로서 사용하는 것이면 어느 것이나 사용할 수 있으나 바람직하기로는 살충제로 널리 사용하고 있어 입수가 용이하고 생산비용적인 측면에서 우수한 클로로피리포스(chlorpyrifos) 또는 디트(deet)를 사용하는 것이 좋다.Insecticide oil in the present invention may be used as long as it is generally used as a raw material of the pesticide, but is preferably widely used as a pesticide, so that it is easy to obtain and excellent in terms of production cost chlorpyrifos (deet) It is good to use
한편 본 발명에서 캡슐의 외부벽재로서 활성물질인 살충제오일의 유해하고 불쾌한 냄새를 마스킹하면서 살충제오일을 외부로부터 보호하여 약효의 효과가 오래 지속되도록 하는 역할을 하는 생분해성 고분자는 폴리카프로락톤, 폴리락틱에시드(polylactic acid), 또는 폴리글리콜라이드(polyglycollide)을 사용할 수 있다.On the other hand, the biodegradable polymer which plays a role of protecting the insecticide oil from the outside while protecting the insecticide oil from the outside while masking the harmful and unpleasant odor of the active material insecticide oil as the outer wall material of the capsule is polycaprolactone, polylactic Acid (polylactic acid), or polyglycolide (polyglycollide) can be used.
본 발명의 마이크로캡슐 형태의 살충제 제조시 이용하는 유화-확산법의 주요한 장점 중의 하나는 생체 적합한 용매의 사용으로 인체에 해가 거의 없다는 점과 수백 나노미터 이하의 미세 캡슐을 제조할 수 있다는 점이다. 이러한 유화-확산법은 생분해성 고분자 또는 약제를 함유한 용매상과 안정화제를 함유한 수상이 상호 포화 후 열역학적으로 안정한 상태에 있다가 교반에 의해 용매상은 연속상인 수상에 액적의 형태로 평형을 이룬다. 이 때 안정화제는 새로 생성된 계면의 액적에 흡착하며 용매가 자발적으로 물에 유화하지 못하기 때문에 교반이 필수적이다. 용매가 물에 완전히 녹을 수 있을 만큼의 충분한 양의 물을 첨가하면 열역학적 불안정에 의해 용매가 수상으로 확산되며 용질의 이동에 의해 나노미터 크기의 미세 캡슐을 제조할 수 있다.One of the main advantages of the emulsification-diffusion method used in the preparation of the microcapsule type insecticide of the present invention is the use of a biocompatible solvent, which is almost harmless to the human body and can produce microcapsules of several hundred nanometers or less. In this emulsion-diffusion method, a solvent phase containing a biodegradable polymer or drug and a water phase containing a stabilizer are in a thermodynamically stable state after mutual saturation, and by stirring, the solvent phase equilibrates in the form of droplets to the continuous water phase. At this time, the stabilizing agent is adsorbed on the droplets of the newly formed interface and stirring is essential because the solvent does not spontaneously emulsify in water. Adding a sufficient amount of water so that the solvent is completely soluble in water, the solvent diffuses into the aqueous phase due to thermodynamic instability and nanometer sized microcapsules can be prepared by solute migration.
본 발명의 마이크로캡슐 형태의 살충제 제조방법은Insecticide preparation method of the microcapsule type of the present invention
생분해성 고분자 0.1∼1.0 중량부를 용매 10∼20 중량부에 용해시킨 후 살충제오일 0.001∼0.01 중량부를 혼합하는 단계와,Dissolving 0.1 to 1.0 parts by weight of the biodegradable polymer in 10 to 20 parts by weight of a solvent, and then mixing 0.001 to 0.01 parts by weight of an insecticide oil;
전기의 생분해성 고분자와 살충제오일이 혼합된 용액을 안정화제 0.5∼5 중량부가 용해되어 있는 수용액 20∼30 중량부에 포화시키는 단계와,Saturating the solution containing the biodegradable polymer and insecticide oil in an amount of 20 to 30 parts by weight in an aqueous solution in which 0.5 to 5 parts by weight of a stabilizer is dissolved;
전기의 포화된 용액을 5분∼15분 동안 3000∼20000rpm의 교반속도로 유화시키는 단계와,Emulsifying the previously saturated solution at a stirring speed of 3000 to 20000 rpm for 5 to 15 minutes,
전기의 유화된 용액에 물 40∼80 중량부를 첨가하여 용매를 수상으로 확산시키는 단계와,Adding 40 to 80 parts by weight of water to the former emulsified solution to diffuse the solvent into the aqueous phase,
공지의 방법을 이용하여 잔존하는 용매를 제거하는 단계를 포함한다.Removing the remaining solvent using a known method.
폴리카프로락톤(polycaprolactone, PCL), 폴리락틱에시드(polylactic acid), 또는 폴리글리콜라이드(polyglycollide)의 생분해성 고분자는 0.1 중량부 미만 사용하면 캡슐의 형성과 캡슐벽제의 두께가 얇아져 전체적인 캡슐의 물성이 저하되는 문제점이 있고, 1.0 중량부 초과하면 과다한 캡슐벽제의 농도로 인하여 캡슐이 형성 되지 않고 벽제 자체가 서로 응집되어 마이크로 입자가 형성되는 문제가 있어 생분해성 고분자는 0.1∼1.0 중량부를 사용하는 것이 좋다. 또한 클로로피리포스 또는 디트와 같은 살충제오일은 0.001 중량부 미만 사용하면 살충효과가 미미하고, 0.01 중량부 초과 사용하면 캡슐의 형성과 환경의 문제가 있을 수 있으므로 살충제오일은 0.001∼0.01 중량부 사용하는 것이 좋다.Biodegradable polymers of polycaprolactone (PCL), polylactic acid, or polyglycollide are used when less than 0.1 parts by weight of the capsule form and the thickness of the capsule wall becomes thin. There is a problem of deterioration, and if it exceeds 1.0 part by weight, the capsule is not formed due to the excessive concentration of the capsule wall, and the wall itself is agglomerated with each other to form micro particles. Therefore, it is preferable to use 0.1 to 1.0 part by weight of the biodegradable polymer. . In addition, insecticide oils such as chloropyrefoss or dit have a minimal insecticidal effect when used in an amount less than 0.001 part by weight, and when used in an amount exceeding 0.01 part by weight, there may be a problem with the formation of capsules and the environment. It is good.
생분해성 고분자를 용해시키는 용매는 프로필렌카보네이트(propylene carbonate, PC), 에틸아세테이트(ethyl acetate, EA), 메틸렌클로라이드(methylene chloride, MC) 중에서 선택된 1종 또는 2종 이상이 균일하게 혼합되어 혼합용매를 사용할 수 있는데 10 중량부 미만 사용하면 캡슐 벽제의 용해도에 문제가 있고, 20 중량부 초가 사용하면 과량의 용매로 인하여 환경 및 용매제거 단계의 문제가 있어 본 발명에서 용매는 10∼20 중량부 사용하는 것이 좋다.The solvent for dissolving the biodegradable polymer is one or two or more selected from propylene carbonate (PC), ethyl acetate (EA) and methylene chloride (MC), which are mixed uniformly. If less than 10 parts by weight is used, there is a problem in the solubility of the capsule wall, 20 parts by weight of the solvent is used in the present invention because of the problem of environmental and solvent removal step due to excess solvent It is good.
이들 용매는 인체에 해가 없으며, 물리화학적으로 안정하고 물에 부분적으로 녹는 용매이면서 동시에 고분자에 대해서도 용해도가 큰 용매이기 때문에 본 발명의 용매로서 적당하다.These solvents are suitable as the solvents of the present invention because they are harmless to the human body, are solvents that are physicochemically stable and partially soluble in water, and at the same time have high solubility in polymers.
캡슐의 안정화를 위해 사용하는 안정화제는 폴리옥시에틸렌 소르비탄 모노 로우레이트(Polyoxyethylene sorbitan monolaurate), 플로닉(pluronic), 소듐라우리얼설페이트(Sodium Lauryl Sulfate, CH3(CH2)10CH2OSO3Na), 오디움 도데실 디페닐오삭이드 디설포네이트(odium dodecyl diphenyloxide disulfonate), 폴리비닐알코올 (polyvinyl alcohol, PVA) 중에서 선택된 하나를 0.5∼5 중량부 사용하는데 만일 0.5 중량부 미만 사용하면 안정화제의 본연의 역할을 기대할 수 없으며, 5 중량부초과하여 사용하는 경우에는 안정성 부여 효과에 대한 변수가 되지 못하며 도리어 잉여 안정화제가 불순물로 작용하여 캡슐의 제조시 미세입자 형성에 영향을 미치는 문제점이 있다.Stabilizers used to stabilize the capsules are polyoxyethylene sorbitan monolaurate, pluronic, sodium lauric sulfate, CH 3 (CH 2 ) 10 CH 2 OSO 3 Na ), 0.5 to 5 parts by weight of one selected from iodium dodecyl diphenyloxide disulfonate and polyvinyl alcohol (PVA), if less than 0.5 parts by weight of the stabilizer It can not be expected to play a role of the original, when used in excess of 5 parts by weight does not become a variable for the effect of imparting stability, there is a problem that affects the formation of microparticles in the manufacture of capsules because the excess stabilizer acts as an impurity.
마이크로캡슐 제조시 유화단계는 5분∼15분 동안 3000∼20000rpm의 교반속도로 유화하는데 유화시간이 5분 미만, 교반속도가 3000rpm 미만에서는 충분한 유화효과를 기대할 수 없으며, 유화시간이 15분 초과, 교반속도가 20000rpm 초과에서는 뚜렷한 유화효과의 상승이 없으며 미세입자간에 응집이 발생할 수 있는 문제점이 있어 마이크로캡슐 제조시 유화단계는 5분∼15분 동안 3000∼20000rpm의 교반속도로 유화하는 것이 좋다.When preparing the microcapsules, the emulsifying step is emulsified at a stirring speed of 3000 to 20000 rpm for 5 to 15 minutes, but when the emulsifying time is less than 5 minutes and the stirring speed is less than 3000 rpm, a sufficient emulsifying effect cannot be expected. If the stirring speed is more than 20000rpm, there is no obvious emulsification effect and there is a problem that agglomeration may occur between the microparticles. Thus, during the microcapsules preparation, the emulsifying step is preferably emulsified at a stirring speed of 3000 to 20000 rpm for 5 to 15 minutes.
마이크로캡슐 형태의 살충제 제조시 안정화제가 용해되어 있는 수용액은 20 중량부 미만 사용하면 유화시에 유상과 수상사이의 안정화에 문제가 있고, 30 중량부 초과 사용하면 용매가 수상으로 확산 될 수 있는 문제가 있어 본 발명에서 안정화제가 용해되어 있는 수용액은 20∼30 중량부 사용하는 것이 좋다.The aqueous solution in which stabilizer is dissolved in the preparation of microcapsule type insecticide has a problem of stabilization between oil phase and water phase when emulsified, and when used in excess of 30 parts by weight, solvent may diffuse into water phase. In the present invention, it is preferable to use 20 to 30 parts by weight of the aqueous solution in which the stabilizer is dissolved.
용매를 수상으로 확산시키기 위해 유화된 용액에 첨가하는 물은 용매의 물에 대한 용해도에 따라 결정하는데 40 중량부 미만 사용하면 용매가 수상으로 완전히 확산이 이루어지지 않으므로 캡슐의 물성이 저하되어 캡슐 형성에 문제가 있고, 80 중량부 초과 사용하면 전체용매가 수상으로 확산 할 수 있는 최대 포화량을 초과하므로 최종물의 안정성에 문제가 있을 수 있으므로 유화된 용액에 첨가하는 물은 40∼80 중량부 사용하는 것이 좋다.The water added to the emulsified solution to diffuse the solvent into the aqueous phase is determined according to the solubility of the solvent in water. If the amount is less than 40 parts by weight, the solvent does not completely diffuse into the aqueous phase. There is a problem, and if it is used in excess of 80 parts by weight, there is a problem in the stability of the final solvent because the total solvent exceeds the maximum saturation amount that can diffuse into the water phase, it is recommended to use 40 to 80 parts by weight of water added to the emulsified solution good.
이하 본 발명을 실시예에 의거하여 설명하고자 한다. 그러나 이들은 본 발명의 일실시에에 불과한 것으로 이들이 본 발명의 권리범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described based on examples. However, these are only one embodiment of the present invention and they do not limit the scope of the present invention.
<실시예 1><Example 1>
상온에서 에틸아세테이트(EA) 10g에 폴리카프로락톤(PCL) 0.2g을 용해 시킨 후 살충제오일인 클로로피리포스(chlorpyrifos) 0.001g를 혼합하였다. 또한, 상온하에서 유화액을 제조하기 위해 폴리비닐알콜(PVA) 1g을 물 20g에 용해 시킨 후, 살충제오일이 혼합되어 있는 용액을 유화액에 섞은 후 균질화기를 이용하여 6000rpm∼12000rpm으로 5분∼10분 동안 유화시켰다.After dissolving 0.2 g of polycaprolactone (PCL) in 10 g of ethyl acetate (EA) at room temperature, 0.001 g of insecticide oil chloropyrifos (chlorpyrifos) was mixed. In addition, in order to prepare an emulsion at room temperature, 1 g of polyvinyl alcohol (PVA) was dissolved in 20 g of water, and then a solution containing insecticide oil was mixed into the emulsion, and then homogenizer was used at 6000 rpm to 12000 rpm for 5 minutes to 10 minutes. Emulsified.
유화한 상에 물을 40g∼80g을 첨가하여 살충제오일을 함유한 나노캡슐을 제조한 후 제조된 상의 유기용매를 로터리증류기를 이용하여 모두 제거하여 도 1과 같이 수분산 마이크로캡슐 형태의 살충제를 제조하였다.40 g to 80 g of water was added to the emulsified phase to prepare a nanocapsule containing insecticide oil, and then all organic solvents of the prepared phase were removed using a rotary distillation machine to prepare an insecticide in the form of a microcapsules as shown in FIG. It was.
<실시예 2><Example 2>
상온에서 메틸렌클로라이드(MC) 20g에 폴리카프로락톤(PCL) 3.5g을 용해 시킨 후 살충제오일인 디트(deet) 10g를 혼합하였다. 또한, 상온하에서 유화액을 제조하기 위해 폴리비닐알콜(PVA) 0.6g을 물 30g에 용해 시킨 후, 살충제오일이 혼합되어있는 용액을 유화액에 섞은 후 균질화기를 이용하여 6000rpm∼12000rpm으로 5분∼10분 동안 유화시켰다.After dissolving 3.5 g of polycaprolactone (PCL) in 20 g of methylene chloride (MC) at room temperature, 10 g of insecticide oil (deet) was mixed. In addition, in order to prepare an emulsion at room temperature, 0.6 g of polyvinyl alcohol (PVA) was dissolved in 30 g of water, and then a solution containing insecticide oil was mixed into the emulsion, followed by a homogenizer for 5 minutes to 10 minutes at 6000 rpm to 12000 rpm. Emulsified.
유화한 상에 물을 50g∼80g을 첨가하여 살충제오일을 함유한 나노캡슐을 제조한 후 제조된 상의 유기용매를 로터리증류기를 이용하여 모두 제거하여 수분산 마이크로캡슐 형태의 살충제를 제조하였다.50 g to 80 g of water was added to the emulsified phase to prepare a nanocapsule containing insecticide oil, and then all organic solvents of the prepared phase were removed using a rotary distillation to prepare a pesticide in the form of a water-dispersible microcapsule.
<실시예 3><Example 3>
유화제에 사용하는 안정화제의 농도를 표 1과 같이 다르게 사용하는 것을 제외하고는 실시예 1과 동일한 방법을 이용하여 유화제의 함량이 증가함에 따라 수분산 나노캡슐 살충제에 대하여 평균입자크기를 측정하여 그 결과를 하기 표 1에 나타내었다.Except for using different concentrations of stabilizers used in emulsifiers as shown in Table 1, the average particle size of the water-dispersed nanocapsule pesticide was measured by increasing the amount of emulsifier using the same method as in Example 1. The results are shown in Table 1 below.
표 1. 안정화제의 종류에 따른 캡슐 입자크기의 변화Table 1. Changes in Capsule Particle Size According to Stabilizer Types
*광산란 장치(Zeta plus, 미국 Brookhaven사)를 사용하여 측정* Measured using a light scattering device (Zeta plus, Brookhaven, USA)
표 1에서처럼 안정화제의 농도가 증가할수록 캡슐의 입자크기가 감소하였는데 이는 임계 미셀(micelle) 농도하에서 더 많은 미셀의 수를 형성하기 때문이다. 그러나 유화제의 함량이 계속 증가함에 따라 캡슐의 크기가 항상 감소하는 것은 아니다.As shown in Table 1, the particle size of the capsule decreased as the concentration of the stabilizer increased, because it formed more micelles under the critical micelle concentration. However, the capsule size does not always decrease as the amount of emulsifier continues to increase.
<실시예 4><Example 4>
균질화기의 교반속도를 하기 표 2와 같이 변화시켜 상기 실시예 1과 동일한 방법으로 마이크로캡슐 형태의 살충제를 제조하였다. 제조된 수분산 마이크로캡슐 살충제에 대하여 평균입자크기를 광산란 장치(Zeta plus, 미국 Brookhaven사)로 측정하였으며 그 결과를 표 2에 나타내었다.The stirring speed of the homogenizer was changed as shown in Table 2 to prepare a pesticide in the form of microcapsules in the same manner as in Example 1. The average particle size of the prepared water-dispersed microcapsule insecticide was measured by a light scattering apparatus (Zeta plus, Brookhaven, USA) and the results are shown in Table 2.
표 2에 나타난 결과로부터 균질화기의 교반속도가 증가할수록 입자크기가 감소함을 알 수 있다. 이것은 균질화기의 회전속도가 증가할수록 일정한 시간동안 더 많은 전단력이 에멀젼 액적에 가해지므로 액적의 크기가 감소하며 액적으로부터 생성되는 미세 입자의 크기도 감소하기 때문에 캡슐의 입자크기 역시 감소한 것임을 알 수 있었다.From the results shown in Table 2, it can be seen that the particle size decreases as the stirring speed of the homogenizer increases. It was found that the particle size of the capsule was also reduced because the size of the droplets decreased and the size of the fine particles generated from the droplets decreased because more shear force was applied to the emulsion droplets for a certain time as the rotation speed of the homogenizer increased.
표 2. 교반속도에 따른 캡슐 입자크기의 변화Table 2. Variation of Capsule Particle Size with Agitation Speed
본 발명에 의해 생분해성 고분자를 사용하여 유화-확산공정을 통해 살충제오일을 함유하는 수분산 마이크로캡슐 형태의 살충제 제조방법을 제공함으로써 마이크로캡슐공정을 통해 생분해성 고분자를 벽재로 사용하여 살충제오일의 유해하고, 불쾌한 냄새를 마스킹하면서 약효의 효과가 오래 지속되도록 할 수 있다.By using the biodegradable polymer according to the present invention through the emulsification-diffusion process to provide a pesticide oil-containing insecticide manufacturing method in the form of microcapsules by using the biodegradable polymer as a wall material through the microcapsule process harmful to the pesticide oil And, masking the unpleasant odor while the effect of the drug can be long lasting.
또한 물을 용매로 사용하기 때문에 환경오염 문제를 해결하는 환경 친화적인 살충제캡슐로 제조하여 환경문제 해결과 더불어 일반적으로 사용의 폭이 한정 되었던 에어로졸 형태, 매트 형태, 독먹이법 형태 그리고 훈연법 형태의 단점을 보완하여 그 응용 범위를 확대 시킬 수 있는 효과가 있다.In addition, since water is used as a solvent, it is manufactured as an environmentally friendly insecticide capsule that solves the environmental pollution problem. In addition to solving the environmental problem, the aerosol form, mat form, poisonous form, and smoking method, which are generally limited in use, are solved. It is effective to make up for the shortcomings and to extend the scope of its application.
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| KR101596350B1 (en) | 2013-08-30 | 2016-02-22 | (주)국보싸이언스 | urethane-urea composite microcapsule type insecticide |
| KR101586347B1 (en) * | 2014-06-13 | 2016-01-20 | 한국생산기술연구원 | A method for preparation of insect-repelling compostion with improved thermal stabililty by polymer grafting |
| KR102032275B1 (en) * | 2018-04-05 | 2019-10-16 | 안호영 | Nanoscale encapsulation formulation of active ingredient chemicals using multicomponent polymer system |
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| KR102278422B1 (en) * | 2019-10-02 | 2021-07-19 | 안호영 | Pesticide composition comprising nanoscale encapsulation formulation of active ingredient chemicals using multicomponent polymer system |
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| EP0368576A2 (en) * | 1988-11-08 | 1990-05-16 | Kureha Kagaku Kogyo Kabushiki Kaisha | Insecticide comprising a suspension of microcapsules containing chlorpyrifos |
| JPH05238904A (en) * | 1991-12-27 | 1993-09-17 | Takeda Chem Ind Ltd | Pesticide-containing microcapsule and its production |
| KR20000028283A (en) * | 1998-10-30 | 2000-05-25 | 안민동 | Microcapsule insecticide using biodegradable polymeric material |
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| EP0368576A2 (en) * | 1988-11-08 | 1990-05-16 | Kureha Kagaku Kogyo Kabushiki Kaisha | Insecticide comprising a suspension of microcapsules containing chlorpyrifos |
| JPH05238904A (en) * | 1991-12-27 | 1993-09-17 | Takeda Chem Ind Ltd | Pesticide-containing microcapsule and its production |
| KR20000028283A (en) * | 1998-10-30 | 2000-05-25 | 안민동 | Microcapsule insecticide using biodegradable polymeric material |
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